Vat dyestuffs of the anthraquinone series



Patented Sept. 27, 1938 were T )QFFICE VAT nrns'rnrrs or runANTHRAQUINONE 5 SERIES Heinrich Neresheimer and Wilhelm Ruppel,Ludwigshafen-on-the-Rhine, Germany, assignors to General Aniline Works,Inc., New York, N. Y., a corporation of Delaware No Drawing. ApplicationOctober 17, 1936, se-

rial No. 106,197. In Germany October 24,

14 Claims.

The present invention relates to new vat dyestuffs.

We have found that valuable-new vat dyestuffs are obtained by splittingofi hydrogen halide from compounds corresponding to the general formula:

l HXL N Halogen pared according to the process of our copendingapplication Ser. No. 70,406, filed March 23, 1936. The splitting off ofthe hydrogen halide may be effected for example by means of concentratedor comparatively dilute acids or by simple heat ing, if desired in thepresence of a diluent. In

some cases it is of advantage to add an agent capable of binding acids.

The vat dyestuffs obtainable according to our invention are generallyspeaking obtained in very good yields. They have good properties asregards fastness.

Furthermore we have found that vat dyestuffs which yield dyeings havingexcellent fastness to alkali and washing are obtained by treating thedyestuffs obtainable in the above described man-.

ner with alkylating agents. As alkylating agents may be mentioned forexample arylsulphonic acid alkyl esters, alkyl sulphates and alkylhalides; The alkylated dyestuffs mayibe purified if de.-'

sired by treatment with hypochlorite.

The following examples will further illustrate.

how the said invention may be carried out in practice but the inventionis not restricted to these examples. The parts are by Weight.

Example 1 A mixture of partsof the compound obtainable from 1 molecularproportion of P2.- dichlor-1.2-pyrazinoanthraquinone and 1 molecularproportion of 1.2 -diaminoanthraquinone byheating the two components inthe presence of nitrobenzene for some time at 110 C. and filtering offthe red-brown needles formed and 15 parts of nitrobenzene is boileduntil hydrogen chloride no longer escapes. resulting compound isfiltered off by suction,

in pure yellow flocks.

After cooling, thewashed with nitrobenzene, freed from adherentnitrobenzene by means of steam and, dried. The olive green compound thusobtained may be purified by dissolving it in 100 parts of 96 per centsulphuric acid and heating the solution with 10 parts of pyrolusite atabout 90 C. until the dyestuff when diluted with water-is precipitatedThe "solution is then poured onto ice, the excess of pyrolusiteisremoved by boiling with anaddition of sodium bisulphite and the dyestuffis filtered off by suction, washed and dried. 'Ihedyestuif thus obtainedyields with alkaline hydrosulphitesolution a redbrown vat from whichcotton is dyed vivid yellow shades.

The same dyestuif is formed by heating the starting material with 10times its amount of 96 per cent sulphuric acid for a short time at i30cam then further proceeding as described above.

described above are introduced into a mixture,

heated to 200 C., of 100 parts oftrichlorbenziane;

and parts'of anhydrous potash, paratoluene-' sulphonic acid methyl esterbeing added in small amounts'until a sample Withdrawn after'boiling;

for several hours yields from the vatv a yellow cotton dyeing which nolonger changes to brown when spotted with alkali. The dyestuif'isthenwashed with alcohol andwater and dried.- It

dyes cotton powerful yellow shades'fast to washing from'a bluish redVat. f a i The same dyestuff can beprepared by using methyl chloride asthe'aldimethyl sulphate or. kylating agent. Similar dyestuffs areobtainedby-using other alkyl esters of para-toluene sulphonic acid, asfor example the ethyl or chlorethyl esters, insteadof themethyl-ester. I

V Example 2 1 10 parts of the compound obtainablelby intro-v ducing 6.3vpartsof 1.2,-diamino-3-bromanthraquinone into a suspension of 6.6 partsof Pz-dichlor-1.2-pyrazinoanthraquinone in 120 parts of nitrobenzene atC. and then'heatingthe mixture' at about C. until hydrogen chloride, no

longer escapes, are introduced at C. into 100' parts of 96 per centsulphuric acid. Whendis} solution is completed, the mixture is heatedfor a short time at from to -.C cooled 'to, I about 80 C. 10 parts ofpyrolusite being introduced at the latter temperature, .Afterheating atabout 100 C. for a short time, the solution is poured into water. Theseparated yellow dye stuff is very similar to that paragraph ofExample 1. g 1 v V 1 By employing as starting material the: compoundsobtainable from Pz-dichlor-L2-pyrazinodescribed in the first 1 20. 10parts of the dyestuff obtained in themanner' anthraquinone and otherhalogen derivatives of 1.2-diaminoanthraquinone, as for example 1.2-

diaminol-chloranthraquinone, or 2.3-diaminoanthraquinone, similardyestuffs are obtained.

10 parts of the dyestuff obtained according to.

the method described in the first paragraph of this example areintroduced at 200 C. into a mixture of 120 parts of trichlorbenzene and20 parts of potash, 20 parts of para-toluene sulphonic acid ethyl esterbeing added and the mix- Example 3 10 parts of the compound obtainableby introducing at C. 6.3 parts of 1.2.-diamino-3-bromanthraquinone intoa solution of, 7.8 parts of 3-chlor-Pz-dichlor-1.2-pyrazinoanthraquinonein parts of nitrobenzene and heating the mixture for several hours at110 C., are introduced at 160 C. into 100 parts of 96 per cent sulphuricacid. The solution is heated for a short time at 200 C. and is thenworked up in the manner described in Example 2. The dyestuff thusobtained dissolves in concentrated sulphuric acid giving a browncoloration and dyes cotton powerful yellow shades from a red-brown vat.-

By starting from the compounds obtainable from3-chlor-Pz-dichlor-1.2-pyrazinoanthraqui none. and1.2-diaminoanthraquinone or 1.2-diamine-4-chloranthraquinone, or fromthe compound obtainable from 4-chlor-Pz-dichlor-L2-pyrazinoanthraquinone and 1.2diaminoanthraquinone according to Example.14 of our copending application, yellow vat dyestufis having similarproperties are also obtained. The dyestuffs may be alkylated bytreatment with para-toluene sulphonic acid alkyl esters in the mannerdescribed in Example 1.

' Example 4 5.1 parts of 1-mercapto-2-aminoanthraquinone are added at 40C. to a suspension of 6.6 parts of Pz dichlor-1.2-pyrazinoanthraquinonein 150 parts of nitrobenzene, the mixture then being heated for severalhours at from 50 to 60 C. A red-brown compound thus separates withevolution of hydrogen'chloride; the compound is separated in the usualmanner. It-dissolves. in concentrated sulphuric acid giving a carminered coloration. 1

10 parts of the compound thus obtained are introduced at 200 C. into 100parts of sulphuric acid monohydrate. This solution is heated for a shorttime at from 220 to 230 C. its color thus changing from bluish red toolive brown. The whole is worked up and purified in the manner describedin Example 2. The yellow dyestufi obtained dissolves in concentratedsulphuric acid giving a brown coloration and dyes cotton clear yellowshades from a red-brown vat.

If the compound derived from dichlor-pyrazinoanthraquinone andI-amino-Z-mercaptoanthraquinone be employed as starting material, ayellow vat dyestuff is also obtained. 7

10 parts of the dyestuff prepared in the manner described above areintroduced into a mixture, heated to 200 C., of 100 parts oftrichlorbenzene and 20 parts of potash, 20 parts ofpara-toluenesulphonic acid methyl ester then being added and the mixtureheated to boiling for several hours.

- The dyestuff is filtered off by suction at about C. and is washed withalcohol and hot water. It may be purified by treatment with sodiumhypochlorite. It dyes cotton from a violet vat powerful yellow shadesand has very good properties as regards fastness.

Example 5 10 parts of the red-brown compound which can be obtained byintroducing 6.5 parts of P2- dichlor-1.2-pyrazinoanthraquinone at 120 C.into a solution of 5 parts of 1-amino-2-methoxyanthraquinone in parts ofnitrobenzene and heating the mixture for several hours, are introducedat 200 C. into 100 parts of sulphuric acid monohydrate. The solution isheated at 250 C. for a short time and worked up in the manner describedin Example 2. A greenish yellow dyestuff is thus obtained which hasproperties similar to those of the dyestuifs described in the otherexamples.

What we claim is:-

1. Vat dyestufis corresponding to the general formula wherein A and Astand for anthraquinone radicles in which the two linkages shown areattached to adjacent alpha and beta positions, wherein R stands for amember of the group consisting of hydrogen and alkyl, and wherein Xstands for a member of the group consisting of N-R, and sulphur.

2. Vat dyestufis corresponding to the general formula wherein A and Astand for radicles of halogenanthraquinones in which the two linkagesshown are attached to adjacent alpha and beta positions, wherein Rstands fora member of the group consisting of hydrogen and alkyl, andwherein Xstands for a member of I the group consisting of NR, andsulphur.

4. Vat dyestufis corresponding to the formula lN I eneral wherein A andA stand for anthraquinone radicles one of which is halogenated in whichthe two linkages shown are attached to adjacent alpha and betapositions, wherein R stands for a member of the group consisting ofhydrogen and alkyl, and wherein X stands for a member of the groupconsisting of NR, and sulphur.

5. Vat dyestufis corresponding to the general formula R lN lL i Lwherein A and A stand for anthraquinone radicles in which the twolinkages shown are attached to adjacent alpha and beta positions, andwherein R stands for a member of the group consisting of hydrogen andalkyl.

6. Vat dyestuffs corresponding to the general formula JLN 11L which dyescotton yellow shades from a redbrown vat.

8. Vat dyestuffs corresponding to the general formula wherein A and. Astand for the radicles of an-. thraquinoneinwhich thev two linkagesshown are attached to adjacent alpha and beta positions; and wherein Rstands for a member of the group consisting of hydrogen andalkyl. p i V9. Vat dyestuffs corresponding to the general formula e v wherein A andA standifor the radicle of anthraquinone in which the two linkages shownare attached to adjacent alpha and beta positions, and wherein'R standsfor 'alkyl. 7

10. The Vat dyestuff corresponding to theformula brown vat. v

11. Vat dyestuffs corresponding to the general formula I wherein Astands for the radicle of anthraquinone, wherein A stands for ahalogenated anthraquinone radicle in which radicles the two linkagesshownare attached to adjacent alpha and beta positions, wherein R standsfor a member of the group consisting of hydrogen and alkyl, and whereinX stands for a member of the group consisting of N'R and sulphur.

12. Vat dyestufis corresponding to the general formula wherein A standsfor the radicle of anthraqui-- none, wherein A stands for a halogenatedanthraquinone radicle in which radicles the two 40 J which dyes cottonyellow shades froma red- 7 orresponding to the general wherein A standsfor the radicle of anthraquinone, wherein A stands for a halogenatedanthraquinone radicle in which radicles the two linkages shown areattached to adjacent alpha and beta positions and wherein R stands foralkyl.

14'. The vat dyestufi corresponding to the tur mula

which dyes cotton greenish yellow shades from a bluish-red vat.

HEINRICH NERESI-IEIMER. WILHELM RUPPEL.

